Flavoring with 8-p-cymenyl-ethyl ether

ABSTRACT

Described are processes for flavoring foodstuffs, chewing gums, medicinal products and toothpastes using as the essential ingredient 8-p-cymenyl ethyl ether which is synthetically produced and substantially pure.

This application is a divisional of application for United StatesLetters Patent Ser. No. 012,798 filed on Feb. 16, 1979, which in turn,is a divisional of application for United States Letters Patent Ser. No.939,897, filed on Sept. 5, 1978, now U.S. Pat. No. 4,163,068, issued onJuly 31, 1979, which, in turn, is a divisional of application for UnitedStates Letters Patent Ser. No. 872,937, filed on Jan. 27, 1978, now U.S.Pat. No. 4,131,687, issued on Dec. 26, 1978.

BACKGROUND OF THE INVENTION

The instant invention provides novel C₁₀ -terpenyl ethers having thestructure:

    (C.sub.10 -TERPENYL-O-R.sub.1).sub.n

wherein the terpene moiety has one of the structures: ##STR1## and themoiety R₁ is C₁ -C₄ alkyl, C₃ or C₄ alkenyl, C₃ haloalkenyl or C₃alkynyl, and uses thereof for their organoleptic properties inconsumable materials.

Materials which can provide green citrus, limey, lemony, piney, tart,herbaceous, floral, sweet anise, borneol-like, earthy carrot,petitgrain-like, grapefruit, deep woody, animal, sandal-like woody,fruity, floral, camphoraceous, and rosemary-like notes with basil-like,carvone-like, chamomile-like, and vanillin-like nuances and sweatyundertones are known in the art of perfumery. Many of the naturalmaterials which provide such fragrances and contribute desired nuancesto perfumery compositions are high in cost, vary in quality from onebatch to another and/or are generally subject to the usual variations ofnatural products. By the same token materials which can provide sweet,fruity, berry-like, minty, green, herbal, musty, vegetable (especiallycelery), spicey, earthy, anise-like, aniseed, fresh fennel,strawberry-like, citrus peel-like (especially orange peel), citrus,coriander-like, licorice, floral, rosey, woody, parsely,grapefruit-like, cumin-like, eucalyptol-like, cedarwood-like,oakwood-like, lemon juice-like, camphoraceous, blueberry, sassafrass,and rooty aroma notes with nutty, fruity, berry-like, minty, bitter,musty, waxy, green, herbal, woody, vegetable (especially celery-like),earthy, sweet, spicey, anise-like, aniseed, fresh fennel, strawberry,citrus peel (especially orange peel), citrus-like, floral, rosey, woody,parsley grapefruit-like, cumin-like, coriander-like, eucalyptol-like,green pea, lemon juice-like, cedarwood like and steamed oak flavor noteshaving sour effects, astringent effects, mouthfeel effects and bitingeffects are well known in the art of flavoring for foodstuffs,toothpastes, chewing gums and medicinal products. Many of the naturalmaterials which provide such flavor notes and contribute desired nuancesto flavorant compositions are high in cost, vary in quality from onebatch to another and/or are generally subject to the usual variations ofnatural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace enhance or augment the essential flavor and fragrancenotes provided by natural essential oils or compositions thereof.Unfortunately many of these synthetic materials either have the desirednuances only to a relatively small degree or else contribute undesirableor unwanted odor to the compositions. The search for materials which canprovide a more refined licorice-like flavor, for example, has beendifficult and relatively costly in the areas of both natural productsand synthetic products.

Artificial flavoring agents for foodstuffs have received increasingattention in recent years. For many years such food flavoring agentshave been preferred over natural flavoring agents at least in part dueto their diminished cost and their reproducible flavor qualities. Forexample, natural food flavoring agents such as extracts, concentratesand the like are often subject to wide variations due to changes inquality, type and treatment of the raw materials. Such variations can bereflected in the end products and result in unfavorable flavorcharacteristics in said end product. Additionally, the presence of thenatural product in the ultimate food may be undesirable because ofincreased tendency to spoil. This is particularly troublesome in foodand food uses where such products as dips, soups, chips, sausages,gravies and the like are apt to be stored prior to use.

The fundamental problem in creating artificial flavor agents is that theartificial flavor to be achieved be as natural as possible. Thisgenerally proves to be a difficult task since the mechanism for flavordevelopment in many foods, medicinal products, chewing gums andtoothpastes is not completely known. This is noticable in productshaving licorice, citrusy and vegetable flavor characteristicsparticularly.

Even more desirable are products that can serve to substitute fordifficult-to-obtain natural perfumery oils and at the same timesubstitute for natural flavoring ingredients in foodstuffs, chewinggums, medicinal products and toothpastes.

In U.S. Pat. No. 3,993,604 issued on Nov. 23, 1976, Thomas and Ohloffdisclose a process for improving, enhancing, or modifying theorganoleptic properties of perfumes, perfumed products, natural orartificial essential oils which comprises adding thereto a small buteffective amount of at least one compound of the formula: ##STR2##wherein R₄ is hydrogen, alkyl or acyl containing from one up to sixcarbon atoms and the dashed line represents a carbon-carbon single bondor a carbon-carbon double bond. The compounds of U.S. Pat. No. 3,993,604are, however, different in kind insofar as their organoleptic qualitiesand aroma and flavor intensities are concerned from the C₁₀ -terpenylethers of the instant case.

A number of the methyl ethers of C₁₀ -terpenes are known, for example,the methyl ether of Carveol (Beilstein, Vol. VI, syst. No. 510) and1,8-dimethoxy-p-menthane

(Royals, J. Am. Chem. Soc., 71, 2563-71 (1949)). In addition, the methylether of p-cymen-8-ol is known as an oxygenated constituent of theessential oil of black pepper as disclosed in Bull. Soc. Chim. Belg.1975, 84(3), 167-77 (abstracted in Chem Abstracts 83:25073c). The ethylether of p,α-dimethylphenethyl alcohol is disclosed at Chem Abstracts70:57320d.

Burczyk at Chem Abstracts 74:13285z discloses a number of methyl ethersof C₁₀ -terpenes having the following structures: ##STR3##

However, the usefulness for augmenting or enhancing the organolepticproperties of perfumes, perfumed articles, colognes, foodstuffs, chewinggums, toothpastes or medicinal products of the terpene ethers asdisclosed herein is neither expressly nor implicitly set forth in any ofthe references set forth above.

Arctander, "Perfume and Flavor Chemicals (Aroma Chemicals)" 1969,discloses at No. 696 the organoleptic properties of citronellyl vinylether as follows: ##STR4##

"Colorless liquid. Insoluble in water, soluble in alcohol and oils.

Green-foliage-like, Rose-Geranium type, fresh and rather powerful odorof modest tenacity.

Useful in Citrus cologne types, soap perfumes (as a diffusive andrefreshing topnote ingredient), as a supporting item for Geranium notes,etc."

At No. 1961 (Vol. II) of Arctander, methyl citronellyl ether isdisclosed for its organoleptic properties as follows: ##STR5##

"Colorless liquid.

Insoluble in water, soluble in alcohol and oils.

Fresh-rosy, green-leafy type of odor with a "wet vegetable" note ofattractive naturalness. Moderate to poor tenacity.

This ether has been suggested for use in perfume compositions, but it israrely offered commercially, although many ethers of Citronellol,Geraniol, Linalool and related alcohols have been prepared in search ofnew floral-green materials. Quite a large number of these ethers havevery interesting and attractive odors, and it is rather surprising thatvery few are offered commercially.

The title ether could find use in modern fragrances, particularly aspart of novel topnote complexes with Citrus, Galbanum orfresh-herbaceous materials, fruity notes, etc.

It blends very well with Bergamot, Estragon, Basil, Verbena and otherdistinguished topnote materials, and it is tolerated in the perfumecomposition at quite surprising concentrations. In other words, itspleasant level of application has a very considerable "range" from lessthan one percent up to 10 or 15%, in exceptional cases even higher thanthat."

However, nothing in the Arctander references discloses the unexpected,unobvious and advantageous organoleptic properties of the C₁₀ -terpenylethers of the instant invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a section of the GLC profile showing the presence of cis- andtrans-1,8-dimethoxy-p-methane in lemon juice and described in Example I.

FIG. 1 is a section of the GLC profile showing the presence of carvylethyl ether and 8-p-cymenyl ethyl ether in lemon juice as described inExample I.

FIG. 2 represents the Mass Spectrum for carvyl ethyl ether producedaccording to Example I and Example II.

FIG. 3 represents the NMR (nuclear magnetic resonance) spectrum forcarvyl ethyl ether produced according to Examples I and II.

FIG. 4 represents the infrared spectrum for carvyl ethyl ether producedaccording to Examples I and II.

FIG. 5 represents the mass spectrum for 8-p-cymenyl ethyl ether producedaccording to Examples I and III.

FIG. 6 represents the NMR spectrum for 8-p-cymenyl ethyl ether producedaccording to Examples I and III.

FIG. 7 represents the infrared spectrum for 8-p-cymenyl ethyl etherproduced according to Examples I and III.

FIG. 8 is a section of the GLC profile showing the presence of fenchylethyl ether in lemon juice as described in Example I.

FIG. 9 represents the mass spectrum for fenchyl ethyl ether producedaccording to Examples I and IV(B).

FIG. 10 represents the NMR spectrum for fenchyl ethyl ether producedaccording to Examples I and IV(B).

FIG. 11 represents the infrared spectrum for fenchyl ethyl etherproduced according to Examples I and IV(B).

THE INVENTION

It has now been determined that certain C₁₀ -terpenyl ethers are capableof imparting a variety of flavors and fragrances to various consumablematerials and are also capable of augmenting or enhancing a variety offlavors and fragrances of various consumable materials. Briefly ourinvention contemplates augmenting or enhancing the flavors and/orfragrances of such consumable materials as perfumes, perfumed articles,colognes, foodstuffs, chewing gums, toothpastes and medicinal productsby adding thereto a small but effective amount of at least one C₁₀-terpenyl ether having the structure:

    (C.sub.10 -TERPENYL-O-R.sub.1).sub.n

wherein n is 1 or 2 and wherein the terpene moiety has one of thestructures: ##STR6## wherein R₁ is C₁ -C₄ alkyl, C₃ or C₄ alkenyl, C₃haloalkenyl, or C₃ alkynyl.

The C₁₀ -terpenyl ethers of our invention augment or enhance sweet,fruity, berry-like, minty, green, herbal, musty, vegetable (especiallycelery), spicey, earthy, anise-like, aniseed, fresh fennel,strawberry-like, citrus peel-like (especially orange peel), citrus,coriander-like, licorice, floral, rosey, woody, parsely,grapefruit-like, cumin-like, eucalyptol-like, cedarwood-like,oakwood-like, lemon juice-like, camphoraceous, blueberry, sassafrass,and rooty aroma characteristics and nutty, fruity, berry-like, minty,bitter, musty, waxy, green, herbal, woody, vegetable (especiallycelery-like), earthy, sweet, spicey, anise-like, aniseed, fresh fennel,strawberry, citrus peel (especially orange peel), citrus-like, floral,rosey, woody, parsley, grapefruit-like, cumin-like, coriander-like,eucalyptol-like, green pea-like, lemon juice-like with sour andastringent mouthfeel and biting effects insofar as augmenting orenhancing the aroma or taste of foodstuffs, toothpastes, medicinalproducts and chewing gums. The C₁₀ -terpinyl ethers of our inventionalso augment or enhance the green citrus, limey, lemony, piney, tart,herbaceous, floral, sweet anise, borneol-like, earthy carrot,petitgrain-like, grapefruit, deep woody animal, sandal-like woody,fruity, floral, camphoraceous, and rosemary/lavander-like notes ofperfumes, perfumed articles and colognes and augment, enhance or impartbasil-like, carvone-like, chamomile-like, and/or vanillin-like nuanceswith sweaty undertones.

Examples of the C₁₀ -terpenyl ethers of our invention and theirorganoleptic characteristics are as follows:

                                      TABLE I                                     __________________________________________________________________________    STRUCTURE   NAME OF   FLAVOR          FRAGRANCE                               OF COMPOUND COMPOUND  CHARACTERISTICS CHARACTERISTICS                         __________________________________________________________________________     ##STR7##   Geranyl butyl ether                                                                     Citrus, floral, rosey aroma characteristics with                              citrus, nutty, floral, rosey and bitter flavor                                character- istics                                                                             A green citrus, lemony, floral                                                aroma                                    ##STR8##   Carvyl ethyl ether                                                                      A woody, green, parsley- like, celery-like and                                grapefruit-like aroma characteristic with woody,                              green, green pea-like, celery- like, citrus flavor                            charac- teristics and a sour and astringent                                                   An earthy, carrot topnote giving                                              way to a petitgrain character with                                            basil/ carvone nuances                   ##STR9##   8-p-cymenyl-ethyl ether                                                                 An herbal, coumarin-like and green aroma                                      characteristic with herbal, cumin-like, lemon                                 juice-like, green, and oily flavor character-                                 istics          A sweet, phenolic,  cymene-like,                                              acetophenone- like aroma with a                                               musty, vanilla, anthranilate note        ##STR10##  fenchyl ethyl ether                                                                     A woody, cedarwood-like, oakwood-like, lemon                                  juice-like, camphoraceous, herbaceous, citrus-like,                           blueberry-like, sassafrass and rooty                                          aroma characteristic with woody, cedarwood-like,                              steamed oak, camphoraceous, herbaceous, citrusy,                              woody, blueberry, sassafrass-like and rooty flavor                            characteristics and a sour, mouthfeel and                                     astringent effect.                                                                            A sweet, camphor- aceous, minty,                                              herbaceous, woody, green aroma with                                           a eucalyptus-like undertone.             ##STR11##  bornyl methyl ether       Camphoraceous, herbal, rosemary/lave                                          ndar and borneol-like aroma              ##STR12##  carvyl methyl ether                                                                     A carrot, parsley-like, earthy and herbal aroma                               character- istic with sweet, carrot-like, earthy,                             celery-like, herbal, parsley-like flavor character-                           stics and a biting effect                                                                     A fresh, earthy, carrot topnote                                               giving way to a woody, carvone-like                                           araway, basil note                       ##STR13##  bornyl ethyl ether                                                                      A camphoraceous, woody, cedarwood-like,                                       eucalyptol-like, and blueberry-like                                           aroma characteristic with camphora- ceous, woody,                             eucalyptol-like, blueberry flavor characteristics                             and an astringent character                                                                   A grape- fruit topnote which fades                                            quickly to sour and acrid having                                              ultimately a sour, fruity, floral                                             aroma with chamomile nuances.            ##STR14##  3-allyloxy-2(10)- pinene                                                                A sweet, anise-like, green, woody and floral aroma                            characteristic with an anise, green and woody                                 flavor characteristic                                                                         A strong, sweet, anisic, borneol-lik                                          e note with piney and herbaceous                                              nuances                                  ##STR15##  2-(2-propynyloxy)- 2(10)-pinene                                                         Aniseed, phenyl, coriander, fruity, berry and                                 citrus peel aroma and flavor characteristics                                                  A sweet, floral aroma with a                                                  vanillin sweetness and a borneol,                                             sweaty undertone                         ##STR16##  3(2-chloroallyloxy)- 2(10)-pinene                                                       Sweet, aniseed-like, fresh phenyl, fruity,                                    strawberry, orange peel and citrusy aroma and                                 flavor characteristics                                                                        A fatty, creosote-like, citrusy,                                              linalyl acetate- like aroma with                                              musty and phenolic notes                 ##STR17##  3-(methallyloxy- 2(10)-pinene                                                           A citrus, licorice and spicey aroma characteristic                            with bitter flavor characteristics                                                            A fruity, anisi lemony aroma with a                                           wood nuance                              ##STR18##  α-terpinyl methyl ether                                                           A sweet, vegetable celery- like), spicey aroma                                character- istic with an earthy nuance and a woody,                           celery-like, earthy flavor characteristic with                                sweet and spicey nuances                                                                      A tart, limey, terpineol- like                                                note                                     ##STR19##  1,8-dimethoxy-p- menthane                                                               A sweet, fruity and minty aroma characteristic with                           green and  musty nuances and a nutty, fruity and                              minty flavor characteristic with bitter, musty,                               waxy and green nuances                                                                        A citrusy note modified by a sweet,                                           sandal-like-woody note                   ##STR20##  1,8-diethoxy-p- menthane                                                                Woody aroma character and woody and bitter flavor                             characteristics A green, citrus/lemony, woody           __________________________________________________________________________                                          aroma                               

The 1,8-dimethoxy-p-menthane can exist as a mixture of the cis and transisomers thereof or can be used as the "cis" isomer having the structure:##STR21## or the "trans" isomer having the structure: ##STR22##

The C₁₀ -terpenyl ethers of our invention can be produced using any oneof several known techniques. Thus, the terpenyl alcohol can be reactedwith a lower alkanol in the presence of an acid catalyst such asparatoluenesulfonic acid at reflux conditions. As a further example,8-p-cymenol may be reacted with an excess of ethanol (e.g. from 2 up to10-fold excess) in the presence of p-toluenesulfonic acid, and thereaction mass may then be refluxed for a period of from 2 up to 10hours. By the same token carvyl ethyl ether may be produced by reactingethanol with carveol, the ratio of ethanol:carveol being about 1 moleethanol:0.1 moles carveol, and the reaction may take place in thepresence of p-toluenesulfonic acid.

The ethers so useful in our invention may also be formed by reacting thecorresponding terpenic alcohol with the appropriate sulfate in thepresence of sodium hydride in anhydrous media and in the presence of aninert solvent such as dimethyl formamide. Thus, for example, fenchylalcohol is reacted with diethyl sulfate, the fenchyl alcohol and diethylsulfate being in a molar proportion of about 1:1 in the presence ofsodium hydride and dimethyl formamide.

Compounds having the generic structure: ##STR23## wherein R₂ representsC₃ or C₄ alkenyl, C₃ haloalkenyl or C₃ alkynyl, may be prepared byreacting pinocarveol with the appropriate organic halide. This reactionis carried out under the influence of a base comprising the step ofplacing the reactants for the process and the base, respectively, in twoimmiscible phases; an organic phase and either (i) an aqueous base phaseor (ii) a solid base phase with the reactants being locatedsubstantially entirely in the first mentioned organic phase and the basebeing located substantially entirely in the second mentioned phase; andadding to the two phase system a "phase transfer agent" which may be oneor more of several organic quaternary ammonium salts.

Specific examples of "phase transfer agents" useful in our invention areas follows:

Tricapryl methyl ammonium chloride;

Cetyl trimethyl ammonium bromide; and

Benzyl trimethyl ammonium hydroxide.

In general, the "phase transfer agents" most preferred have the genericformula: ##STR24## wherein at least one of R₁ ', R₂ ', R₃ ' and R₄ ' isC₆ -C₁₄ aryl, C₆ -C₁₀ aralkyl, C₆ -C₂₀ alkyl, C₆ -C₁₄ aralkyl and C₆-C₂₀ alkenyl, and the other of R₂ ', R₃ ' and R₄ ' is alkyl such asmethyl, ethyl, n-propyl, i-propyl, 1-butyl, 2-butyl, 1-methyl-2-propyl,1-pentyl and 1-octyl and Z- is an anion such as chloride, bromide andhydroxide.

This process of our invention is carried out in an inexpensive solventwhich is inert to the reaction system, such as toluene, benzene,o-xylene, m-xylene, p-xylene, ethyl benzene, n-hexane, cyclohexane,methylene dichloride and o-dichlorobenzene.

The process of our invention is carried out at a temperature in therange of from about 10° C. up to about 150° C. with a temperature rangeof 30°-120° C. being preferred. The reaction time is inverselyproportional to the reaction temperature, with lower reactiontemperature giving rise to greater reaction times; and, accordingly, thereaction time ranges from about 30 minutes up to about 10 hours.

In the reaction of our invention the mole ratio of pinocarveol toorganic halide is in the range of from 0.5:1.5 up to about 1.5:0.5 witha preferred ratio of pinocarveol to organic halide being from about 1:1up to about 1:1.2.

The mole ratio of base to pinocarveol in the reaction mass may be in therange of from about 0.75:1 up to about 1.5:1 with a preferred ratio ofbase:pinocarveol being from about 1:1 up to about 1.2:1.

The quantity of "phase transfer agent" in the reaction mass based on theamount of pinocarveol in the reaction mass may vary from 0.5 grams permole of pinocarveol up to 25 grams of "phase transfer agent" per mole ofpinocarveol with a preferred concentration of "phase transfer agent"being in the range of from about 2.5 up to about 7.5 grams of "phasetransfer agent" per mole of pinocarveol.

This reaction of our invention is preferably carried out at atmosphericpressure since that is the most convenient condition. However, lower orhigher pressures can be used without detrimentally affecting theultimate yield of desired product. The particular base used in thereaction is not critical, but, preferred are sodium hydroxide andpotassium hydroxide.

The individual C₁₀ -terpenyl ethers of our invention can be obtained inpure form or in substantially pure form by conventional purificationtechniques. Thus, the products can be purified and/or isolated bydistillation, extraction, crystallization, preparative chromatographictechniques and the like. It has been found desirable to purify the C₁₀-terpenyl ethers by fractional distillation in vacuo.

When the C₁₀ -terpene ethers of our invention are used as food flavoradjuvants, the nature of the co-ingredients included with said C₁₀-terpene ethers in formulating the product composition will also serveto alter, modify, augment or enhance the organoleptic characteristics ofthe ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter," "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste."

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible, non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine, and a flavoring composition whichincorporates one or more of the C₁₀ -terpene ethers of our invention,and in addition, sweetening agents which may be sugars, includingsucrose or dextrose and/or artificial sweeteners such as cyclamates orsaccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising, broadly, stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like,and sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids,carbohydrates; starches, pectins, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buttersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal,beta,beta-dimethylacrolein, methyl n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptenal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, benzaldehyde, damascone, α-damascone, damascenone,acetophenone, 2-heptanone, o-hydroxyacetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methylfurfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanol, 2-heptanol,trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol,1-penten-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpin hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl carpylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alphamethylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyldiphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethylnaphthalene, tridecane, trimethylnaphthalene, undecane,caryophyllene, α-phellandrene, β-phellandrene, p-cymene 1-alpha-pinene,beta-pinene, dihydrocarveol; pyrazines such as 2,3-dimethylpyrazine,2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oilssuch as jasmine absolute, cassia oil, cinnamon bark oil, black pepperoleoresin, oil of black pepper, rose absolute, orris absolute, oil ofcubeb, oil of coriander, oil of pimento leaf, oil of patchouli, oil ofnutmeg, lemon essential oil, safran oil, Bulgarian rose, capsicum, yarayara and vanilla; lactones such as γ-nonalactone; sulfides, e.g., methylsulfide and other materials such as maltol, and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane), piperine,chavicine, and piperidine.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the C₁₀ -terpene ethers of ourinvention by not covering or spoiling the organoleptic properties (aromaand/or taste) thereof; (ii) be non-reactive with the C₁₀ -terpene ethersof our invention and (iii) be capable of providing an environment inwhich the C₁₀ -terpene ethers can be dispersed or admixed to provide ahomogeneous medium. In addition, selection of one or more flavoringadjuvants, as well as the quantities thereof will depend upon theprecise organoleptic character desired in the finished product. Thus, inthe case of flavoring compositions, ingredient selection will vary inaccordance with the foodstuff, chewing gum, medicinal product ortoothpaste to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid products, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount of C₁₀-terpene alkyl, alkenyl, haloalkenyl, and alkynyl ethers and diethersemployed in a particular instance can vary over a relatively wide range,depending upon the desired organoleptic effects to be achieved. Thus,correspondingly, greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored (e.g. with a spiceflavor or a specific black pepper-like flavor) is relatively bland tothe taste, whereas relatively minor quantities may suffice for purposesof enhancing the composition merely deficient in natural flavor oraroma. The primary requirement is that the amount selected be effective,i.e., sufficient to alter, modify or enhance the organolepticcharacteristics of the parent composition, whether foodstuff per se,chewing gum per se, medicinal product per se, toothpaste per se, orflavoring composition.

The use of insufficient quantities of C₁₀ -terpene alkyl, alkenyl,haloalkenyl, and alkynyl ethers and diethers will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases maydisrupt the flavor-aroma balance, thus proving self-defeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of C₁₀ -terpene alkyl,alkenyl, haloalkenyl, and alkynyl ethers and diethers ranging from asmall but effective amount, e.g., 0.5 parts per million up to about 100parts per million based on total composition, are suitable.Concentrations in excess of the maximum quantity stated are not normallyrecommended since they fail to provide commensurate enhancement oforganoleptic properties. In those instances wherein the C₁₀ -terpenealkyl, alkenyl, haloalkenyl, and alkynyl ethers and diethers are addedto the foodstuff as an integral component of a flavoring composition, itis of course essential that the total quantity of flavoring compositionemployed be sufficient to yield an effective C₁₀ -terpene alkyl,alkenyl, haloalkenyl, and alkynyl ether and diether concentration in thefoodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the C₁₀ -terpene alkyl, alkenyl,haloalkenyl, and alkynyl ethers and diethers in concentrations rangingfrom about 0.1% up to about 15% by weight based on the total weight ofthe said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the C₁₀ -terpene alkyl, alkenyl,haloalkenyl, and alkynyl ethers and diethers with, for example, gumarabic, gum tragacanth, carrageenan and the like, and thereafterspray-drying the resultant mixture whereby to obtain the particularsolid product. Pre-prepared flavor mixes in powder form, e.g., afruit-flavored powder mix, are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like, and C₁₀ -terpene alkyl,alkenyl, haloalkenyl, and alkynyl ethers and diethers in a dry blenderuntil the requisite degree of uniformity is achieved.

It is presently preferred to combine with the C₁₀ -terpene alkyl,alkenyl, haloalkenyl, and alkynyl ethers and diethers of our invention,the following adjuvants:

Oil of Cubeb;

Phellandrene;

β-phellandrene;

Oil of Coriander;

Oil of Pimento Leaf;

Oil of Patchouli;

Alpha Pinene;

Beta Pinene;

Beta-caryophyllene;

Dihydrocarveol;

Piperonal;

Piperine;

Chavicine;

Piperidine;

Oil of Black Pepper;

Black Pepper Oleoresin;

Capsicum;

Oil of Nutmeg.

Cardamom Oil;

Clove Oil;

Spearmint Oil; and

Oil of Peppermint.

The C₁₀ -terpene alkyl, alkenyl, haloalkenyl, and alkynyl ethers anddiethers of our invention can be used to contribute, green citrus,limey, lemony, piney, tart, herbaceous, floral, sweet anise,borneol-like, earthy carrot, petitgrain, grapefruit, deep woody animal,sandal-like woody, fruity, floral, camphoraceous, androsemary/lavendar-like notes with basil-like, carvone-like,chamomile-like, vanillin-like nuances and sweaty undertones. Asolfactory agents the C₁₀ -terpene alkyl, alkenyl, haloalkenyl, andalkynyl ethers and diethers of our invention can be formulated into orused as components of a "perfume composition."

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, alcohols, aldehydes, ketones,nitriles, ethers, and frequently hydrocarbons which are admixed so thatthe combined odors of the individual components produce a pleasant ordesired fragrance. Such perfume compositions usually contain: (a) themain note of the "bouquet" or foundation-stone of the composition; (b)modifiers which round-off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation, and substances whichretard evaporation; and (c) top-notes which are usually low-boiling,fresh-smelling materials.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereof,can be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of the C₁₀ -terpene alkyl, alkenyl, haloalkenyl, and alkynylether and diether of this invention which will be effective in perfumecompositions depends on many factors, including the other ingredients,their amounts and the effects which are desired. It has been found thatperfume compositions containing as little as 2% of the C₁₀ -terpenealkyl, alkenyl, haloalkenyl, and alkynyl ethers and diethers of thisinvention, or even less, can be used to impart an interesting citrusyand/or petitgrain aroma to soaps, cosmetics, and the other products. Theamount employed can range up to 50% or higher and will depend onconsiderations of cost, nature of the end product, and the effectdesired on the finished product and particular fragrance sought.

The C₁₀ -terpene alkyl, alkenyl, haloalkenyl, and alkynyl ethers anddiethers of this invention can be used alone or in a perfume compositionas a olfactory component in detergents and soaps, space odorants anddeodorants; perfumes; colognes, toilet waters; bath salts; hairpreparations such as lacquers, brilliantines, pomades, and shampoos;cosmetic preparations such as creams, deodorants, hand lotions, and sunscreens; powders such as talcs, dusting powders, face powder, and thelike. When used as an olfactory component of a perfumed article, aslittle as 0.01% of one or more of the C₁₀ -terpene alkyl, alkenyl,haloalkenyl, and alkynyl ethers and diethers will suffice to impart aninteresting citrusy and/or petitgrain aroma. Generally, no more than0.5% is required.

In addition, the perfume composition can contain a vehicle or carrierfor the C₁₀ -terpene alkyl, alkenyl, haloalkenyl, and alkynyl ethers anddiethers alone or with other ingredients. The vehicle can be a liquidsuch as an alcohol such as ethanol, a glycol such as propylene glycol,or the like. The carrier can be an absorbent solid such as a gum orcomponents for encapsulating the composition.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I

5600 Pounds of lemons are halved, juiced and strained. The juice isdiluted with a 50% volume of food-grade ethyl alcohol and centrifuged.The supernatant liquid is continuously extracted with Freon 11 for 24hours. The extract is dried and concentrated. It is then separated intoacidic, basic and neutral fractions by solvent extraction.

The methyl ester derivatives of the acidic components are then preparedby reaction with BF₃ -methanol methylation reagent. Analysis of thisfraction results in the identification of the cis and trans isomers of1,8-dimethoxy-p-menthane. A section of the GLC profile which includespeaks for these isomers is set forth in FIG. 1A. FIG. 24 represents theNMR spectrum for 1,8-dimethoxy-p-menthane thus trapped out. FIG. 25represents the IR spectrum for 1,8-dimethoxy-p-menthane thus trappedout.

Column chromatography of the neutral fraction on 5% water-deactivatedsilica gel using varying amounts of ether in isopentane results in 120fractions which are bulked according to the GC profiles. Analysis of onesuch bulked fraction by GC-MS and subsequent trapping and analysis ofthe unknown components by NMR and IR results in the identification ofcarvyl ethyl ether and 8-p-cymenyl ethyl ether. Further separation ofthis fraction by GC area trapping, and analysis of the area traps byGC-MS results in the identification of fenchyl ethyl ether.

    ______________________________________                                        GC Conditions:                                                                             Column: 500' × 0.03" Stainless steel,                                   open tubular, SF-96                                                           Program: 70-190° C. at 1° C./min.                               Nitrogen Flow Rate: 12 ml/min.                                   ______________________________________                                    

FIG. 1 represents a section of the GLC profile which includes peaks forcarvyl ethyl ether and 8-p-cymenyl ethyl ether. FIG. 8 sets forth asection of the GLC profile which includes the peak for fenchyl ethylether.

FIG. 2 represents the mass spectrum for carvyl ethyl ether thus trappedout. FIG. 3 represents the NMR spectrum for carvyl ethyl ether thustrapped out. FIG. 4 represents the infrared spectrum for carvyl ethylether thus trapped out. FIG. 5 represents the mass spectrum for8-p-cymenyl ethyl ether thus trapped out. FIG. 6 represents the NMRspectrum for 8-p-cymenyl ethyl ether thus trapped out. FIG. 7 representsthe infrared spectrum for 8-p-cymenyl ethyl ether thus trapped out. FIG.9 represents the mass spectrum for fenchyl ethyl ether thus trapped out.FIG. 10 represents the NMR spectrum for fenchyl ethyl ether thus trappedout.

EXAMPLE II Synthesis of Carvyl Ethyl Ether

    ______________________________________                                        Reaction:                                                                      ##STR25##                                                                    Chemicals                                                                     ______________________________________                                        Carveol            0.5 moles = 76 g                                           Ethanol            5 moles = 230 g                                            Paratoluene                                                                   sulfonic acid      3.13 g                                                     ______________________________________                                    

Procedure

The above chemicals are placed in a 500 ml, three-necked, round bottomflask equipped with a mechanical stirrer, Friedrich's condenser andheating mantle. The mixture is heated to reflux for 24 hours, thencooled and added to 100 ml. of cold 5% NaOH solution. The aqueous layeris drawn off and the remaining layer is washed with 3×50 ml of distilledwater and dried over anhydrous Na₂ SO₄. 37.78 Grams of crude material isleft.

The title compound is purified by distillation through a short column.Eight fractions are collected as follows:

    ______________________________________                                                 Pressure                                                             Fraction (mm Hg)  Temperature  Grams                                          ______________________________________                                        1        3           55° C.                                                                           1.47                                           2        3        75           0.90                                           3        3        78           7.65                                           4        3        85           4.50                                           5        3        87           1.18                                           6        3        92           3.24                                           7        3        96           2.81                                           8        3        98           1.17                                                                          22.92 grams                                    ______________________________________                                    

Fraction 8 is further purified by trapping the two major peaks from an8'×1/8" 20% Carbowax 20 M column. (Conditions: programmed at 80°-190° C.at 4° C./min.) The peaks are identified as isomers of2,8-diethoxy-p-menthane.

Fraction 3 is analyzed via MS-GC. The major peak is the title compound.The compound is trapped from an 8'×1/8" 10% Carbowax 20 M packed column(programmed at 80°-190° C. at 4° C./min).

The mass spectrum for the carvyl ethyl ether is set forth in FIG. 2. TheNMR spectrum for carvyl ethyl ether is set forth in FIG. 3. The IRspectrum for carvyl ethyl ether is set forth in FIG. 4.

EXAMPLE III Synthesis of 8-p-Cymenyl Ethyl Ether

    ______________________________________                                        Reaction:                                                                      ##STR26##                                                                    Chemicals                                                                     ______________________________________                                        8-p-cymenol      44.5 g (0.297 moles)                                         ethanol          136.6 g (2.97 moles)                                         paratoluene                                                                   sulfonic acid    1.86 g                                                       ______________________________________                                    

Procedure

The above chemicals are placed in a 250 ml, three-necked, round-bottomflask equipped with a Friedrich's condenser, mechanical stirrer andheating mantle. The resulting mixture is heated to reflux until the GCindicates that the reaction has gone to completion. The reaction mass iscooled to room temperature and neutralized with a saturated Na₂ CO₃solution. Then the aqueous phase is extracted with three 100 ml portionsof methylene chloride. The methylene chloride extract is dried overanhydrous Na₂ SO₄ and stripped on a rotary evaporator. The mixture isfractionated on a gas chromatograph, and three major peaks are eluted,two of them match 8-p-cymenol and the third is unknown. The titlecompound is purified by preparative gas chromatography.

Conditions

12'×0.375" 10% SE-30 column;

140° C. Isothermal;

Feed Rate: 250 μl/min

A total of 0.35 g is collected for evaluation (purity=98.82%).

The mass spectrum for 8-p-cymenol ethyl ether is set forth in FIG. 5.The NMR spectrum for 8-p-cymenol ethyl ether is set forth in FIG. 6. TheIR spectrum for 8-p-cymenol ethyl ether is set forth in FIG. 7.

EXAMPLE IV(A) Synthesis of Isobornyl Ethyl Ether

    ______________________________________                                        Reaction:                                                                      ##STR27##                                                                     Chemicals                                                                    ______________________________________                                        Isoborneol   1 mole = 154 g                                                   NaH          1 mole = 48 g (50% in mineral oil)                               Diethyl sulfate                                                                            1.1 mole = 169.4 g                                               DMF (dimethyl                                                                              500 ml.                                                          formamide)                                                                    Triethyl borate                                                                            80.3 g                                                           ______________________________________                                    

Procedure

The NaH and DMF (400 ml) are added to a two liter, round-bottom flaskequipped with an N₂ bubbler, vented Friedrich's condenser, mechanicalstirrer and additional funnel. CaCl₂ Drying tubes are placed on all openends. N₂ Is bubbled into the flask to evacuate the air. Isoborneol isthen dissolved in 100 ml of DMF and placed in the addition funnel. Theisoborneol is then added dropwise to the reaction mass. When theisoborneol addition is complete, the mixture is heated until no more H₂is given off. The reaction mass is then cooled to room temperature, andthe diethyl sulfate is added dropwise. The reaction is slightlyexothermic. After all of the diethyl sulfate is added, GC analysisindicates that less than 0.3% of the diethyl sulfate is present.

The mixture is cooled to room temperature, and one liter of water isslowly added thereto over a period of one hour. Two layers are present,the top layer being drawn off and saved. The aqueous layer is extractedwith two 250 ml portions of diethyl ether. The ether layer is combinedwith the top layer and dried over anhydrous Na₂ SO₄ ; then stripped byrotary evaporator. 152.97 Grams of crude material remains, GCyield=54.89%.

The 152.97 grams of crude material plus 80.3 grams (0.55 moles) oftriethyl borate are placed in a 500 ml flask equipped with a 12"Vigreaux column and distillation head. The contents are heated atatmospheric pressure until the pot temperature reaches 160° C. (within 1hour).

The resulting material is then transferred to a fractional distillationapparatus and fractionally distilled (distillation conditions: 62°-68°C. at 2.0-2.4 mm Hg pressure).

The total weight of combined fractions 3-8 amounts to 50.65 g (actualyield--28%) of material over 94% pure. Fraction #8 is subjected to MS,NMR and IR analyses. The NMR analysis indicated that the composition isisobornyl ethyl ether.

EXAMPLE IV(B) Synthesis of Fenchyl Ethyl Ether

    ______________________________________                                        Reaction:                                                                      ##STR28##                                                                     Chemical                                                                     ______________________________________                                        Fenchyl alcohol                                                                            154 g (1M)                                                       Sodium hydride                                                                             48 g of 50% in mineral oil (1M)                                  Diethyl sulfate                                                                            169.4 g (1M)                                                     DMF (dimethyl                                                                              500 ml                                                           formamide)                                                                    ______________________________________                                    

Procedure

The reaction is carried out and extracted in the same manner asdescribed in Example IV(A), supra (SYNTHESIS OF ISOBORNYL ETHYL ETHER).The yield of crude material after the ether is stripped is 170.80 g.G.C. yield=43.4%.

The 170.8 g of crude material is added to 74.2 g of triethyl borate anddistilled at atmospheric pressure as in Example IV(A).

The material left in the pot is then transferred to a fractionaldistillation apparatus and distilled at 66°-67° C. at 5 mm Hg pressure.Fraction #5 is subjected to MS, NMR and IR analyses. The percent yieldbased on Fractions 4-6 combined is 23.3%.

FIG. 9 represents the mass spectrum for fenchyl ethyl ether producedaccording to Example IV(B). FIG. 10 represents the NMR spectrum forfenchyl ethyl ether. FIG. 11 represents the infrared spectrum forfenchyl ethyl ether.

What is claimed is:
 1. A process for flavoring a foodstuff or chewinggum to impart a herbal, coumarin-like and green aroma characteristicwith herbal, cumin-like, lemon juice-like, green, and oily flavorcharacteristics comprising the step of adding to a foodstuff or chewinggum from 0.5 ppm up to about 100 ppm of synthetically producedsubstantially pure 8-p-cymenyl ethyl ether having the structure:##STR29##